α-Imino metal carbenes are versatile intermediates in organic synthesis, and have broad applications in the assembly of divergent N-heterocycles. However, the catalytic enantioselective desymmetrization based on α-imino metal carbenes has not been developed to date. Herein, we disclose an enantioselective desymmetrizing C(sp²)–H functionalization of azide-ynamides via α-imino copper carbenes, leading to the efficient assembly of divergent chiral indoloazepines in generally moderate to excellent yields with high enantioselectivities. Notably, this reaction represents the first enantioselective desymmetrization based on α-imino metal carbenes. Further synthetic transformations and biological tests show the potential utility of this method. Moreover, computational studies are employed to elucidate the reaction mechanism and the origin of enantioselectivity.

α-亚氨基金属卡宾是有机合成中的多功能中间体，在不同的N-杂环的组装中具有广泛的应用。然而，基于α-亚氨基金属卡宾的催化对映选择性去对称化迄今为止尚未开发出来。在此，我们公开了通过α-亚氨基铜卡宾对叠氮-炔酰胺进行对映选择性去对称化C(sp ² )–H官能化，从而以中等至优异的产率和高对映选择性有效组装不同的手性吲哚氮杂卓。值得注意的是，该反应代表了第一个基于 α-亚氨基金属卡宾的对映选择性去对称反应。进一步的合成转化和生物测试显示了该方法的潜在效用。此外，还采用计算研究来阐明反应机理和对映选择性的起源。